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Ultra-bright, efficient and stable perovskite light-emitting diodes

Nature volume 611, pages 688–694 (2022)Cite this article

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Abstract

Metal halide perovskites are attracting a lot of attention as next-generation light-emitting materials owing to their excellent emission properties, with narrow band emission1,2,3,4. However, perovskite light-emitting diodes (PeLEDs), irrespective of their material type (polycrystals or nanocrystals), have not realized high luminance, high efficiency and long lifetime simultaneously, as they are influenced by intrinsic limitations related to the trade-off of properties between charge transport and confinement in each type of perovskite material5,6,7,8. Here, we report an ultra-bright, efficient and stable PeLED made of core/shell perovskite nanocrystals with a size of approximately 10 nm, obtained using a simple in situ reaction of benzylphosphonic acid (BPA) additive with three-dimensional (3D) polycrystalline perovskite films, without separate synthesis processes. During the reaction, large 3D crystals are split into nanocrystals and the BPA surrounds the nanocrystals, achieving strong carrier confinement. The BPA shell passivates the undercoordinated lead atoms by forming covalent bonds, and thereby greatly reduces the trap density while maintaining good charge-transport properties for the 3D perovskites. We demonstrate simultaneously efficient, bright and stable PeLEDs that have a maximum brightness of approximately 470,000 cd m−2, maximum external quantum efficiency of 28.9% (average = 25.2 ± 1.6% over 40 devices), maximum current efficiency of 151 cd A−1 and half-lifetime of 520 h at 1,000 cd m−2 (estimated half-lifetime >30,000 h at 100 cd m−2). Our work sheds light on the possibility that PeLEDs can be commercialized in the future display industry.

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Fig. 1: Emergence of in situ core/shell perovskite with BPA treatment.
Fig. 2: Surface passivation of BPA ligand.
Fig. 3: Luminescent property and defect passivation with BPA treatment.
Fig. 4: EL characteristics of PeLEDs with BPA treatment.

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The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (Ministry of Science, ICT and Future Planning) (NRF-2016R1A3B1908431). G.-S.P was supported by the DGIST R&D Program (22-CoE-NT-02) by the Korea government (Ministry of Education and Ministry of Science, ICT and Future Planning).

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Author notes

  1. These authors contributed equally: Joo Sung Kim, Jung-Min Heo

Authors and Affiliations

  1. Department of Materials Science and Engineering, Seoul National University, Seoul, Republic of Korea

    Joo Sung Kim, Jung-Min Heo, Gyeong-Su Park, Seung-Je Woo, Dong-Hyeok Kim, Jinwoo Park, Sang-Hwan Park, Eojin Yoon & Tae-Woo Lee

  2. Research Institute of Advanced Materials, Seoul National University, Seoul, Republic of Korea

    Gyeong-Su Park & Tae-Woo Lee

  3. Institute of Next-Generation Semiconductor Convergence Technology, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu, Republic of Korea

    Gyeong-Su Park

  4. Cavendish Laboratory, Department of Physics, University of Cambridge, Cambridge, UK

    Changsoon Cho & Neil C. Greenham

  5. Advanced Nano Research Group, Korea Basic Science Institute (KBSI), Daejeon, Republic of Korea

    Hyung Joong Yun

  6. PEROLED Co. Ltd., Seoul, Republic of Korea

    Seung-Chul Lee

  7. Soft Foundry, Seoul National University, Seoul, Republic of Korea

    Seung-Chul Lee & Tae-Woo Lee

  8. School of Chemical and Biological Engineering, Institute of Engineering Research, Seoul National University, Seoul, Republic of Korea

    Tae-Woo Lee

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Contributions

J.S.K., J.-M.H. and T.-W.L. initiated and designed the study. J.S.K. and J.-M.H. fabricated LED devices and analysed data. G.-S.P. performed the TEM measurements. H.J.Y. conducted the UPS and XPS analysis. S.-J.W. and D.-H.K. conducted the temperature-dependent PL and photoluminescence quantum efficiency analysis. S.-J.W. and C.C. conducted the optical simulation of the devices with guidance from N.C.G. J.P. assisted with analysis of the TCSPC data. S.-C.L. provided support for characterization of the materials. S.-H.P. and E.Y. assisted with the fabrication of LED devices. T.-W.L. supervised the work. J.S.K. drafted the first version of the manuscript, with assistance from J.-M.H. and T.-W.L. All authors discussed the results and commented on the manuscript.

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Correspondence to Tae-Woo Lee.

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Nature thanks Lina Quan, Zhanhua Wei and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Fig. 1 Morphology of in situ particle perovskite thin films.

SEM images of perovskite thin films made of 1.2M precursor solution with a, 0% (3D), b, 2.5%, c, 5%, d, 10% (in situ particle) molar ratio of BPA molecule relative to PbBr2. e, HAADF-STEM image and EDS elemental maps of P (green), Br (yellow), and Pb (red), respectively. f, HAADF-STEM image and EDS elemental maps of a single perovskite grain showing the uniform dispersion of P (green), Br (yellow), and Pb (red) on the grain.

Extended Data Fig. 2 Morphological characterization during in situ core/shell particle synthesis process.

a, SEM image of a perovskite thin film (after 1s of reaction time with BPA-THF solution) showing small grains cracked out from large 3D grain. b, STEM image of 50 nm-size perovskite crystal during in situ core/shell synthesis process. Yellow arrows indicate the defective perovskite surfaces that can be bound with BPA. c, HR-TEM image of another perovskite crystal showing ultra-small nanocrystals segregated during in situ core/shell synthesis process. Insets: Magnified HR-TEM images of ultra-small nanocrystals taken from the white-boxed regions labelled C1 and C2. d, e, High-resolution HAADF-STEM images of single perovskite nanograins with decreasing grain size. Magnified HAADF-STEM images of the grain surfaces (D1, D2, E1, E2, F1, F2, G1, G2) demonstrate that the BPA shell coverages on the grain surfaces gradually increase and the defective surface regions decrease as the grain size decreases.

Extended Data Fig. 3 Characterization of perovskite/BPA core/shell interface.

a, High-resolution HAADF-STEM image of single perovskite grain formed during in situ core/shell synthesis process. b, c, Atomic-scale HAADF-STEM (b) and ABF-STEM (c) images of the boxed area denoted in a. d,e, Magnified HAADF-STEM (d) and ABF-STEM (e) images of the boxed area shown in b and c to indicate the positions of EELS acquisition. f, EEL spectra acquired at the atomic positions labelled A, B, and C in d, e. g, EEL spectrum in the energy-loss range of the N-K and O-K edges acquired at the position labelled C. The O-K peak indicates the presence of BPA shells, but N-K peak is simply a background signal from the silicon nitride TEM window grid.

Extended Data Fig. 4 SEM image of low-concentration (0.6 M) perovskite thin films with different reaction time between BPA solution and perovskite thin film.

a, 3D perovskites without reaction, b, 1 s, c, 15 s, d, 30 s of exposure time to BPA-THF solution before spin-drying. Coloured regions indicate initial large crystals (red) and split nanograins (green). e, Schematic illustration of the growth process of BPA macroparticle domain and perovskite crystal forming in situ core/shell structure.

Extended Data Fig. 5 HAADF-STEM analysis of  in situ core/shell perovskites.

a, TEM image and b, c, magnified HAADF-STEM images of in situ core/shell perovskite thin films. d, HAADF-STEM image of in situ core/shell grains and EDS elemental maps of P (red), Pb (yellow), and Br (green), respectively. The EDS maps clearly show the uniform dispersion of P (red) over macrograins. e, HAADF-STEM image of single macrograins consists of  in situ core/shell nanoparticles. f, EDS spectrum acquired at the location of the red circled region in e.

Extended Data Fig. 6 Photoluminescence characteristics of perovskite thin films.

a, PL spectra and b, normalized PL spectra of quartz/perovskite thin film measured in integrating sphere. c, External PLQE versus internal radiation efficiency (ηrad) (i.e. internal quantum efficiency, IQE) of perovskite film calculated considering the influence of perovskite reabsorption30,31. The external PLQE of the in situ core/shell structure was 46%, which corresponds to an IQE of 88%. d–i, Temperature-dependent PL spectrum and corresponding integrated PL intensity with calculated activation energy for: d,g, 3D, e,h, in situ particle, f,i, in situ core-shell perovskite thin films.

Extended Data Fig. 7 Current-voltage-luminance characteristics of PeLEDs.

a, Current density versus voltage; b, luminance versus current density; c, normalized EL spectra; d, CIE coordinate of in situ core/shell PeLEDs; e, power efficiency versus luminance; f, current efficiency versus luminance of PeLEDs based on 3D, in situ particle, in situ core/shell structure. g, Angle-dependent EL intensity and h, luminance histogram of PeLEDs based on in situ core/shell structure. i, EQE histogram of the PeLEDs based on in situ core/shell structure with different processing condition. As the temperature of the glove box increases or the A-NCP process is delayed, the grain size of the spin-coated perovskite thin film increases, which slows the penetration of the BPA solution into perovskite crystal and prevents full conversion of them into the in situ core/shell structure.

Extended Data Fig. 8 Large-area devices.

a, Luminance versus voltage; b, EQE versus current density of large-area devices based on in situ core/shell perovskites. c–f, Photographs of large-area devices (pixel size: 120 mm2) operating at: c, < 10 cd m−2; d, 1,000 cd m−2; e, 100,000 cd m−2; and f, 100,000 cd m−2 under daylight, showing uniform emission over the pixel.

Extended Data Fig. 9 Operational lifetime of PeLEDs.

a, Luminance versus time of PeLEDs based on 3D, in situ particle, and in situ core/shell perovskites at initial brightness of 10,000 cd m−2, and b, corresponding driving voltage versus operation time.

Extended Data Table 1 Summarized electrical and luminance characteristics of PeLEDs
Full size table

Supplementary information

Supplementary Information

Supplementary Figs. 1–7, Tables 1–3 and refs.

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Kim, J.S., Heo, JM., Park, GS. et al. Ultra-bright, efficient and stable perovskite light-emitting diodes. Nature 611, 688–694 (2022). https://doi.org/10.1038/s41586-022-05304-w

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